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Brook, G. A., Marais, E., Srivastava, P., & Jordan, T. (2007). Timing of lake-level changes in Etosha Pan, Namibia, since the middle Holocene from OSL ages of relict shorelines in the Okondeka region. Quaternary International, 175(1), 29–40.
Abstract: In 2003 examination of aerial photographs revealed a series of previously unknown relict shorelines on the arcuate ridge, possibly a clay lunette dune, that marks the western boundary of Etosha Pan in Namibia. The shorelines are 120–600m wide and the most prominent extend for tens of km around the lunette dune. The shorelines were examined on the ground in 2004 and an attempt was made to date the three lowest levels at ca. 5, 2.5 and 1m above the present pan surface. The OSL ages obtained indicate higher and more prolonged lake conditions than today at ca. 6.4, 4.0 and 2.1ka with the youngest shoreline sediments resting on an ancient pan surface dating to ca. 13ka. The evidence indicates dry conditions in the pan at ca. 13ka, wetter conditions and higher lake levels in the middle Holocene followed by a decline in lake levels to the present. Periods of inundation were of sufficient duration to produce shorelines at the southwestern end of the pan due to the prevailing northeasterly winds that would have maximized wave action along this section of the pan margin. The Etosha findings, together with other regional paleoclimate data, suggest four periods of increased wetness in SW Africa during the Holocene at 7–5, 4.5–3.5, 2.5–1.7 and ca. 1.0ka. There is widespread evidence for the oldest of these periods suggesting that it was a prominent and widespread interval of wetness. Prior to ca. 8.0ka the climate may have been drier than today.
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Dutova, E. M., Nikitenkov, A. N., Pokrovskiy, V. D., Banks, D., Frengstad, B. S., & Parnachev, V. P. (2017). Modelling of the dissolution and reprecipitation of uranium under oxidising conditions in the zone of shallow groundwater circulation. Journal of Environmental Radioactivity, 178-179, 63–76.
Abstract: Generic hydrochemical modelling of a grantoid-groundwater system, using the Russian software “HydroGeo”, has been carried out with an emphasis on simulating the accumulation of uranium in the aqueous phase. The baseline model run simulates shallow granitoid aquifers (U content 5 ppm) under conditions broadly representative of southern Norway and southwestern Siberia: i.e. temperature 10 °C, equilibrated with a soil gas partial CO2 pressure (PCO2, open system) of 10−2.5 atm. and a mildly oxidising redox environment (Eh = +50 mV). Modelling indicates that aqueous uranium accumulates in parallel with total dissolved solids (or groundwater mineralisation M – regarded as an indicator of degree of hydrochemical evolution), accumulating most rapidly when M = 550–1000 mg L−1. Accumulation slows at the onset of saturation and precipitation of secondary uranium minerals at M = c. 1000 mg L−1 (which, under baseline modelling conditions, also corresponds approximately to calcite saturation and transition to Na-HCO3 hydrofacies). The secondary minerals are typically “black” uranium oxides of mixed oxidation state (e.g. U3O7 and U4O9). For rock U content of 5–50 ppm, it is possible to generate a wide variety of aqueous uranium concentrations, up to a maximum of just over 1 mg L−1, but with typical concentrations of up to 10 μg L−1 for modest degrees of hydrochemical maturity (as indicated by M). These observations correspond extremely well with real groundwater analyses from the Altai-Sayan region of Russia and Norwegian crystalline bedrock aquifers. The timing (with respect to M) and degree of aqueous uranium accumulation are also sensitive to Eh (greater mobilisation at higher Eh), uranium content of rocks (aqueous concentration increases as rock content increases) and PCO2 (low PCO2 favours higher pH, rapid accumulation of aqueous U and earlier saturation with respect to uranium minerals).
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Bullock, L. A., & Parnell, J. (2017). Selenium and molybdenum enrichment in uranium roll-front deposits of Wyoming and Colorado, USA. Journal of Geochemical Exploration, 180, 101–112.
Abstract: Sandstone uranium (U) roll-front deposits of Wyoming and Colorado (USA) are important U resources, and may provide a terrestrial source for critical accessory elements, such as selenium (Se), molybdenum (Mo), and tellurium (Te). Due to their associated toxicity, MoSeTe occurrences in roll-fronts should also be carefully monitored during U leaching and ore processing. While elevated MoSe concentrations in roll-fronts are well established, very little is known about Te occurrence in such deposits. This study aims to establish MoSeTe concentrations in Wyoming and Colorado roll-fronts, and assess the significance of these deposits in an environmental and mineral exploration context. Sampled roll-front deposits, produced by oxidized groundwater transportation through a sandstone, show high MoSe content in specific redox zones, and low Te, relative to crustal means. High Se concentrations (up to 168ppm) are restricted to a narrow band of alteration at the redox front. High Mo content (up to 115ppm) is typically associated with the reduced mineralized nose and seepage zones of the roll-front, ahead of the U orebody. Elevated trace element concentrations are likely sourced from proximal granitic intrusions, tuffaceous deposits, and local pyritic mudstones. Elevated MoSe content in the sampled roll fronts may be regarded as a contaminant in U in-situ recovery and leaching processing, and may pose an environmental threat in groundwaters and soils, so extraction should be carefully monitored. The identification of peak concentrations of MoSe can also act as a pathfinder for the redox front of a roll-front, and help to isolate the U orebody, particularly in the absence of gamma signatures.
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Robin, V., Beaufort, D., Tertre, E., Reinholdt, M., Fromaget, M., Forestier, S., et al. (2020). Fate of dioctahedral smectites in uranium roll front deposits exploited by acidic In Situ Recovery (ISR) solutions. Applied Clay Science, 187, 105484.
Abstract: In Situ Recovery (ISR) is the most important process of uranium production in the world (50%). It consists of an injection of a leaching solution into a permeable mineralized aquifer (sandstone), pumping of the solution after dissolution of the ore minerals and recovery of the uranium from the pregnant solution in a surface plant. In this context, the fate of swelling clay minerals such as smectites is of main importance due to their role in the mobility of cationic elements by diverse geochemical processes such as ion-exchange reactions or dissolution. The present study details analysis of dioctahedral smectites before and after in-situ leaching by acidic (H2SO4) ISR solutions. Samples were collected from two sedimentary basins hosting some of the main uranium roll front deposits exploited by acidic ISR (Tortkuduk deposit, Shu-Saryssu basin, Kazakhstan, and Dulaan Uul and Zoovch Ovoo deposits, Sainshand basin, Mongolia). Scanning Electron Microscope and X-Ray Diffraction analysis revealed that dioctahedral smectite is a ubiquitous mineral in all analyzed samples, before and after acidification, and revealed a difference of crystal chemistry of the smectites between deposits of Kazakhstan (beidellite type) and Mongolia (montmorillonite type). Chemical analysis and semi-quantification of the smectites before and after acidification also revealed a difference in chemical reactivity, with a higher dissolution of montmorillonite layers compared to beidellite ones, and the importance of ion-exchange reactions. These findings are consistent with literature data obtained on model systems. The persistence of dioctahedral smectites after several years of acidification is crucial for the understanding of geochemical processes during uranium production or remediation of the aquifers. Finally, based on the analysis of samples from U-deposits hosted in both sedimentary basins, a schematic model of the impact of acid solutions on dioctahedral smectite was proposed.
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Romeo, N., Mabry, J., Hillegonds, D., Kainz, G., Jaklitsch, M., & Matsumoto, T. (2022). Developments of a field gas extraction device and krypton purification system for groundwater radio-krypton dating at the IAEA. Applied Radiation and Isotopes, 189, 110450.
Abstract: The long-lived radio-krypton isotope 81Kr (t1/2 = 2.29 × 105 yr) is an ideal tracer for old groundwater age dating in the range of 105–106 years which goes beyond the reach of radio-carbon (14C) age dating. Analytical breakthrough made over the last two decades in Atom Trap Trace Analysis (ATTA) has enabled the use of this isotope with extremely low abundance (81Kr/Kr = 6 × 10−13) to be used as a practical dating tool for very old groundwater. The International Atomic Energy Agency aims to provide this new isotope tool for better groundwater resource management of Member States and developed a field sampling device to collect dissolved gas samples from groundwater and a system to separate and purify trace amounts of krypton from the gas samples for the ATTA analysis. The design, setup and performances of our sampling and purification systems are described here. Our system can produce a high purity aliquot of about 5 μL of krypton from 5 L of air sample (recovery yield of >90%). The samples made by our system were confirmed to be acceptable for the ATTA analysis.
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Zhou, Y., Li, G., Xu, L., Liu, J., Sun, Z., & Shi, W. (2020). Uranium recovery from sandstone-type uranium deposit by acid in-situ leaching – an example from the Kujieertai. Hydrometallurgy, 191, 105209.
Abstract: The factors influencing uranium recovery in water-rock systems during acid in-situ leaching (ISL) were studied at the Kujieertai uranium deposit in Xinjiang. Using an ISL unit, a field leach trial (FLT) had been carried out to test the sequential effects of a leaching solution without oxidant (H2SO4 solution 4–8 g/L) and a leaching solution with oxidant (H2SO4 3–7 g/L, and Fe (III) 2–6 g/L). The observation of the leaching process revealed clearly defined stages of uranium release from the solid mineral to solution. Uranium mobilization from solid mineral into solution can be described in four stages. At the beginning of the acid ISL process, there was no oxidant to be added to the leaching solution and the desorption of hexavalent uranyl ions in the open pores, as well as dissolution of hexavalent uranium minerals, led to a short-term peak in the pregnant solution, which happened while pH decreased from about 5.3 to 2.62. Following the depletion of the adsorbed hexavalent uranium and a decline in uranium dissolution intensity, the addition of Fe(III) facilitated the oxidation of tetravalent uranium, which enabled intensive uranium mobilization again. During this process, the dissolution of uranium had a strong positive correlation with the reduction of Fe(III) and Eh in the leach solution. Beside hydrochemical factors, the deportment of uranium was also an important factor affecting uranium recovery. Uranium located in the open pores can be completely exposed to the solution and the mobilization intensity was significantly affected by hydrogeochemical conditions; but the uranium present in microfissures and in the ore matrix could not be fully exposed to the solution, so, their dissolution intensity was primarily controlled by corrosion and permeability of the ore. In general, the hydrogeochemical conditions and the deportment of uranium were the external and internal factors that significantly affected the dissolution and recovery of uranium in the early and middle stages of the FLT. However, in the latest stages, due to uranium depletion, enhancing the chemical potential of the leaching solution, specifically acidity and/or the amount of oxidant, had little improvement on uranium recovery.
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Ola, I., Drebenstedt, C., Burgess, R. M., Mensah, M., Hoth, N., Okoroafor, P., et al. (2024). Assessing petroleum contamination in parts of the Niger Delta based on a sub-catchment delineated field assessment. Environmental Monitoring and Assessment, 196(6), 585.
Abstract: The Niger Delta in Nigeria is a complex and heavily contaminated area with over 150,000 interconnected contaminated sites. This intricate issue is compounded by the region’s strong hydrological processes and high-energy environment, necessitating a science-based approach for effective contamination assessment and management. This study introduces the concept of sub-catchment contamination assessment and management, providing an overarching perspective rather than addressing each site individually. A description of the sub-catchment delineation process using the digital elevation model data from an impacted area within the Delta is provided. Additionally, the contamination status from the delineated sub-catchment is reported. Sediment, surface water and groundwater samples from the sub-catchment were analyzed for total petroleum hydrocarbons (TPH) and polycyclic aromatic hydrocarbons (PAHs), respectively. Surface sediment TPH concentrations ranged from 129 to 20,600 mg/kg, with subsurface (2-m depth) concentrations from 15.5 to 729 mg/kg. PAHs in surface and subsurface sediment reached 9.55 mg/kg and 0.46 mg/kg, respectively. Surface water exhibited TPH concentrations from 10 to 620 mg/L, while PAHs ranged from below detection limits to 1 mg/L. Groundwater TPH concentrations spanned 3 to 473 mg/L, with total PAHs varying from below detection limits to 0.28 mg/L. These elevated TPH and PAH levels indicate extensive petroleum contamination in the investigated sediment and water environment. Along with severe impacts on large areas of mangroves and wetlands, comparison of TPH and PAH concentrations with sediment and water quality criteria found 54 to 100% of stations demonstrated exceedances, suggesting adverse biological effects on aquatic and sediment biota are likely occurring.
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Hebert, B., Baron, F., Robin, V., Lelievre, K., Dacheux, N., Szenknect, S., et al. (2019). Quantification of coffinite (USiO4) in roll-front uranium deposits using visible to near infrared (Vis-NIR) portable field spectroscopy. Journal of Geochemical Exploration, 199, 53–59.
Abstract: Coffinite (USiO4) is a common uranium-bearing mineral of roll-front uranium deposits. This mineral can be identified by the visible near infrared (Vis-NIR) portable field spectrometers used in mining exploration. However, due to the low detection limits and associated errors, the quantification of coffinite abundance in the mineralized sandstones or sandy sediments of roll-front uranium deposits using Vis-NIR spectrometry requires a specific methodological development. In this study, the 1135 nm absorption band area is used to quantify the abundance of coffinite. This absorption feature does not interfere with NIR absorption bands of any other minerals present in natural sands or sandstones of uranium roll-front deposits. The correlation between the 1135 nm band area and coffinite content was determined from a series of spectra measured from prepared mineral mixtures. The samples were prepared with a range of weighted amounts of arenitic sands and synthetic coffinite simulating the range of uranium concentration encountered in roll-front uranium deposits. The methodology presented in this study provides the quantification of the coffinite content present in sands between 0.03 wt% to 1 wt% coffinite with a detection limit as low as 0.005 wt%. The integrated area of the 1135 nm band is positively correlated with the coffinite content of the sand in this range, showing that the method is efficient to quantify coffinite concentrations typical of roll-front uranium deposits. The regression equation defined in this study was then used as a reference to predict the amount of natural coffinite in a set of mineralized samples from the Tortkuduk uranium roll-front deposit (South Kazakhstan).
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Weerahewa, J., Timsina, J., Wickramasinghe, C., Mimasha, S., Dayananda, D., & Puspakumara, G. (2023). Ancient irrigation systems in Asia and Africa: Typologies, degradation and ecosystem services. Agricultural Systems, 205, 103580.
Abstract: CONTEXT Ancient irrigation systems (AISs) have been providing a multitude of ecosystem services to rural farming and urban communities in Asia and Africa, especially in arid and semi-arid climatic areas with low rainfall. Many AISs, however have now been degraded. A systematic analysis of AISs on their typologies, causes of degradation, and their ecosystem services is lacking. OBJECTIVE The objective of this review was to synthesize the knowledge on AISs on their typologies, status and causes of degradation, ecosystem services and functions, and identify gaps in research in Asia and Africa. METHOD A critical review of peer-reviewed journal papers, conference and workshop proceedings, book chapters, grey literature, and country reports was conducted. Qualitative and quantitative information from journal papers were used to conceptualize the typologies and analyze the status and causes of degradation, and ecosystems services and functions provided by the AISs. RESULTS AND CONCLUSION Based on the review, we classified AISs into three groups by source of irrigation water: Rainwater harvesting system (RHS) with small reservoirs, ground water based system, and floodwater based system. The RHSs, which used to receive reliable rainfall and managed by well cohesive social organizations for their maintenance and functioning in past, have now been silting due to extreme rainfall pattern and breakdown of the cohesive organizations in recent decades. In ground water based systems, indiscriminate development of deep tube wells causing siltation of channels has been a major challenge. In floodwater irrigation systems, irregular rainfall in the highlands and the breakage of irrigation structures by destructive floods were the main causes of degradation. Lack of maintenance and increased soil erosion, inadequate skilled manpower, and declining support from the government for repair and maintenance were the main causes of degradation of all AISs. The main ecosystem service provided by all AISs is water for agriculture. In tank- and pond-based systems, fish farming is also practiced. Tank irrigation systems provide various types of provisioning, regulatory, cultural and supporting services, especially in India and Sri Lanka. Ground water based systems provide water for domestic purposes and various cultural services. Floodwater based systems provide water for power generation and wildlife habitat maintenance and help in flood control. SIGNIFICANCE The knowledge generated through the review provide evidence-based information, and help aware governments, private sectors and development agencies for improved policy planning and decision making, and prioritizing the restoration, rehabilitation, and management of various AISs.
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Boulesteix, T., Cathelineau, M., Deloule, E., Brouand, M., Toubon, H., Lach, P., et al. (2019). Ilmenites and their alteration products, sinkholes for uranium and radium in roll-front deposits after the example of South Tortkuduk (Kazakhstan). Journal of Geochemical Exploration, 206, 106343.
Abstract: The approximate determination of average Ra/U disequilibria in orebodies is one of the most common causes of errors in U reserve estimations. In roll-front deposits, the disequilibria are however frequently distributed following complex geometries, which must be fully understood to prevent major U reserve overestimates and costly unproductive extractive operations. The processes responsible for disruption of the radioactive equilibria and the U and Ra carriers in such complex natural systems remain poorly constrained. In this contribution, we propose an innovative approach, mixing orebody to sub-grain scale studies to unravel the distribution of U and Ra and the processes responsible for their concentration and uncoupling. Using mineral separations, gamma spectrometry and mineral-chemical analyses, we identified the Fe-Ti clusters (altered ilmenite + pyrite/marcasite) as the microsites for coffinite precipitation and Ra concentration. To understand the influence of such clusters on the distribution of U and Ra at the deposit scale, whole-rock Ra/U disequilibria were measured and mapped at a series of ten drill holes along a profile crosscutting the studied roll-front. The main Ra/U disequilibria are encountered around the mineralization in low U content zones. They are controlled by two main processes. (1) In the oxidized zones, the immobility of 230Th with respect to the U produces patches of Ra disequilibria (carried by the altered U minerals). (2) In the immediate vicinity of the roll-front, the dissolution of the mineralization produces an Ra flux trapped by the alteration products of ilmenites, as definitely confirmed by direct SIMS measurements. Such a process is responsible for the Ra disequilibria envelope located downstream of the richest ores, also known as Ra halo. The highest Ra/U ratios correspond to oxidized upstream samples, but most other high Ra/U ratios are from reduced downstream samples close to the mineralization. Such a low to medium U content envelope with high Ra/U ratios constitutes the main cause of U reserve overestimations.
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